1. Field of the Invention
The invention relates to new derivatives of 1-arylpyrazoles which have some valuable properties either as pesticides or as intermediates to make other pesticides. The invention further pertains to compositions of said compounds and methods, using said compounds either as intermediates to make other pesticides, or for the control of arthropod pests, in particular to the application of said compounds or compositions in agricultural methods of use or for animal protection, particularly as pesticides, for controlling arthropods.
2. Description of the Related Art
International Patent Publication No. WO 87/03781 and European Patent Publication Nos. 0295117, 0154115, 0201852 describe insecticidal 1-(substituted phenyl)pyrazoles. Other prior art is also found in the text of these patent applications or the patents issued therefrom.
International Patent Publication Nos. WO 93/06089 and WO 94/21606 also describe insecticidal 1-(4-SF5 substituted phenyl) heterocycles which may be pyrroles as well as imidazoles or pyrazoles. The teaching of these patents is not substantially different from International Patent Publication No. WO 87/03781 or from European Patent Publication No. 0295117 as far as pyrazoles are concerned.
Various pesticidal pyrazoles have been disclosed in various patents or patent applications: European 0418016, 0403309, 0352944; U.S. Pat. Nos. 5,104,994, 5,079,370, 5,047,550, 5,232,940, 4,810,720, 4,804,675, 5,306,694, 4,614,533, 5,187,185, 5,223,525; WO 93/06089, 94/21606.
Due to the many existing pests and crops and conditions of attacks of crops by pests, there is a need for further novel pesticidal compounds.
It is an object of the present invention to provide new pesticidal compounds of the 1-arylpyrazole family together with processes for their preparation.
A second object of the present invention is to provide pesticidal compositions and pesticidal methods of use of the pesticidal pyrazole compounds against arthropods, especially insects, particularly in agricultural or horticultural crops, forestry, veterinary medicine or livestock husbandry, or in public health.
A third object of the present invention is to provide very active compounds, with broad spectrum pesticidal activity, as well as compounds with selective special activity, e.g., aphicidal, miticidal, foliar insecticidal, soil insecticidal, systemic, antifeeding or pesticidal activity via seed treatment.
These and other objects, which are met in whole or in part by the instant invention, shall become readily apparent from the description of the invention which follows.
This invention embraces novel chemical compounds having an insecticidal, miticidal, nematocidal or anthelminthic activity.
The invention relates to compounds having the general formula (I): 
wherein:
R31 and R32 may individually be OR20, S(O)nR20, or N(R20)(R21); or R31 and R32 may also connect to form O[C(R22)(R23)]mO, S(O)n[C(R22)(R23)]mS(O)a, O(CH2)mS(O)n, O[C(R22)(R23)]m(NR20), S(O)n[C(R22)(R23)]m(NR20), NR21[C(R22)(R23)]mNR20, NR21[C(O)(CH2)m]NR20;
m is an integer from 1 to 5;
when m is greater than one, the groups [C(R22)(R23)] may be the same or different;
R20, R21 may individually be H, alkyl, aryl, benzyl, allyl, propargyl;
R22, R23 may individually be H; halogen; OH; NH2; COOR20; C(O)NH2; C(O)N(R20)(R21); C(S)NH2; OC(O)N(R20)(R21); CN; NO2; C(S)N(R20)(R21); alkyl which may optionally be substituted with OH, NH2, halogen, CN, NO2, COOR20, C(O)NH2, C(S)NH2; S(O)balkyl; alkoxy; S(O)cR20;
R4 is R26; S(O)dR26; S(xe2x95x90R27)(xe2x95x90NR28)R26;
R26 is alkyl optionally substituted with one or more halogen which may be the same or different;
R5 is NH2, alkylamino where the alkyl may be substituted with NO2, halogen, CN, alkoxycarbonyl, OH, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or carbamoyl; or R5 is a radical having the formula: 
wherein
R4, R12, R13, R14, R15, Z and R33 are identical to R4, R12, R13, R14, R15, Z and R33, respectively, in formula (I) above;
R27 is NR28, O or a lone pair of electrons;
R28 is selected from H; C1-C6 alkyl; C1-C6 haloalkyl; COR24; S(O)eR24; COOR24; C(O)N(R20)(R21); C(O)SR24; C(S)OR24; SO2NR20R21; P(O)q(R20)(R21); P(O)q(OR20)(OR21); C(xe2x95x90NR20)NR20R21; C(xe2x95x90NR20)(OR21); C(S)N(R20)(R21); C(O)C(O)R20; C(O)C(O)OR20; C(O)C(O)NR20R21; and C(O)NR20SO2R21;
q is 0 or 1;
R24 is alkyl optionally substituted with NO2, CN, halogen, alkoxy, amino, alkoxycarbonyl or OH;
Z is N or Cxe2x80x94R16;
R12, R13, R14, R15 and R16 may individually be H; halogen; SF5; CN; NO2; R25; S(O)fR25; OH; OR25; N(R36)(R37); CON(R25)(R37); N3 (azido);
R36 and R37 may individually be H, alkyl;
R25 may be alkyl optionally substituted with one or more halogen which may be the same or different;
R33 is C1 to C3 alkyl, optionally substituted by one or more halogen, NO2, alkoxy, CN, COOH, COO-alkyl, C(O)NH2; and
n, a, b, c, d, e and f, which are the same or different, are each 0, 1 or 2; and pesticidally acceptable salts thereof.
The stereoisomers, e.g. diastereomers and optical isomers, having the formula (I) are included in the invention as well.
In this description, the term xe2x80x98alkylxe2x80x99 when unqualified generally means a straight- or branched-chain alkyl having from one to six carbon atoms. The term xe2x80x98arylxe2x80x99 means C6-C10 aryl, e.g. phenyl or naphthyl, optionally bearing one or more substituents selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, CN, NO2, C1-C6 haloalkyl and C1-C6 haloalkoxy.
Preferred compounds of formula (I) include those wherein R13 and R15 are or halogen; R12 is halogen; R16 is H or halogen; and/or R14 is halogen, SF5, R25, S(O)fR25 or OR25. Compounds in which R12 is chlorine, R13 and R15 are H, R14 is CF3, and Z is Cxe2x80x94Cl, are especially preferred.
Compounds of formula (I) wherein R4 is S(O)dR26 and Z is Cxe2x80x94R16 are also referred.
The symbol m is preferably 2, 3 or 4, more preferably 2 or 3, most preferably 2.
Other preferred compounds of formula (I) are those wherein:
R26 is CH3 or CH2CH3; Z is Cxe2x80x94R16; R13 and R15 are H; R12 is halogen; R16 is H or halogen; R14 is CF3, OCF3 or SF5; and/or R33 is CH3.
Still most preferred compounds of formula (I) are those wherein:
R31 and R32 may individually be OCH3; OC2H5; SCH3; SC2H5; R31 and R32 may also connect to form OCH2CH2O; O(CH2)3O; S(CH2)2S; S(O)(CH2)2S; S(O)(CH2)2S(O); S(O)2(CH2)2S(O); S(O)2(CH2)2S(O)2; S(CH2)2O; S(O)(CH2)2O; S(O)2(CH2)2O; O(CH2)[CH(CH2OH)]O; O(CH2)[C(CH2OH)(CH2OH)]O; OCH(COOCH3)CH(COOCH3)O; OCH(COOC2H5)CH(COOC2H5)O; OCH2C(COOCH3)(COOCH3)CH2O; OCH2C(COOC2H5)(COOC2H5)CH2O; OCH2CH(CH3)O; SCH2CH2NH; OCH2CH(CH2CH2OH)O; OCH2C(CH2OH)2CH2O; OCH2CH(CH2SCH3)O; or OCH2CH(CH2SOCH3)O; particularly when R4 is S(O)dR26; R26 is CH3 or CH2CH3; Z is Cxe2x80x94R16; R13 and R15 are H; R12 is halogen; R16 is H or halogen; R14 is CF3, OCF3 or SF5; and R33 is CH3.
Preferably, the compounds of formula (I) have one or more of the following features:
R12 is halogen;
X is Cxe2x80x94C1;
R13 and R15 are H;
R14 is CF3 or SF5;
R5 is NH2, CH3NH, or CH3CH2NH;
R4 is CH3S(O), CH3S(O)2 or CH3S;
R31 and R32 are OCH3 or connect to form OCH2CH2O; OCH2CH(CH3)O; S(CH2)2S; S(O)(CH2)2S; S(O)(CH2)2S(O); S(O)2(CH2)2S(O)2; O(CH2)[CH(CH2OH)]O; SCH2CH2NH; O(CH2)CH(CH2SCH3)O; O(CH2)CH(CH2SOCH3).
Compounds of the general formula (I) can be prepared by reacting the compounds of the general formula (II): 
wherein R4, R5, R12, R13, R14, R15, Z and R33 are as defined above and R34 is oxygen or sulfur, with a compound (III) having at least one reactive functional group selected from the group consisting of alcohol, thiol, primary amine and secondary amine.
More precisely, the compound (III) may be:
an alcohol of general formula of R20OH;
a thiol of general formula of R20SH;
an amine of general formula of HN(R20)(R21);
or a compound of the formula
HO[C(R22)(R23)]mOH, HS[C(R22)(R23)]mSH, HO[C(R22)(R23)]mSH, HO[C(R22)(R23)]mN(R20)H, HS[C(R22)(R23)]mN(R20)H, or
NHR20[C(R22)(R23)]mNHR21 where R22 and R23 may be the same or different and R20 and R21 may be the same or different.
The reaction of the compound of (II) with the compound of (III) can be achieved by directly reacting the compounds of formula (II) and the compounds (III) in a liquid medium at a temperature in the range from about xe2x88x9235xc2x0 C. to about 250xc2x0 C., preferably from about xe2x88x9210xc2x0 C. to about 150xc2x0 C. Removal of water is preferred. The liquid medium can be achieved either by means of the reactant or with a solvent. Possible solvents for the reaction may be organic solvents including alcohols such as methanol, ethanol, isopropanol; ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane; nitrites such as acetonitrile; aromatic solvents such as toluene, benzene, chlorobenzene; haloalkanes such as chloroform, methylene chloride; amides such as dimethylamide; ketones such as acetone, methylisobutylketone; esters such as ethyl acetate. The amount of reactant is generally between about 50% and about 200% what is required by the reaction (except when a reactant is used as solvent, and then the amount of reactant is much higher). The reaction can be conducted with or without presence of acid catalyst. The acid catalyst can be an inorganic acid such as hydrochloric acid, sulfuric acid; an organic acid such as acetic acid, formic acid, p-toluenesulfonic acid; Lewis acids such as iron (III) chloride, ammonium chloride, boron trifluoride, aluminum chloride, zinc iodide, zinc chloride; acidic ion-exchange resin; clays such as Montmorillonite.
In the process described in the preceding paragraph, when R5 is xe2x80x94NH2 and R34 is oxygen in the starting material of formula (II), in addition to forming a compound of formula (I) in which R5 is xe2x80x94NH2, there can be produced, by reaction with another molecule of the starting material of formula (II), a compound of formula (I) in which R5 is a radical of formula (Ia) set forth hereinabove. Both products are active as pesticides.
The sulfoxide and sulfone compounds of the formula (I), i.e. the compounds in which n, a, b, c, d, e or f is 1 or 2, can also be prepared by oxidation of the corresponding sulfide using appropriate oxidation reagents including but not limited to peroxide, such as hydrogen peroxide, t-butyl peroxide; peracids such as meta-chloroperbenzoic acid; acyl nitrates such as acetyl nitrate and other nonperoxide agents such as sodium periodate, sodium perborate, manganese oxide, potassium permanganate, N-bromosuccinimide, preferably hydrogen peroxide and sodium periodate.
In cases, such as in oxyketal sulfide, where mild conditions are required sodium periodate is the preferred sulfoxidation agent.
The following non-limiting Examples illustrate the invention.